Isotopic substitutions largely affect the dielectric relaxation dynamics of hydrogen-bonded liquid water; yet, the role of the altered molecular masses and nuclear quantum effects has not been fully established. To disentangle these two effects we study the dielectric relaxation of light (H216O), heavy (D216O) and heavy-oxygen (H218O) water at temperatures ranging from 278 to 338 K. Upon 16O/18O exchange, we find that the relaxation time of the collective orientational relaxation mode of water increases by 4-5%, in quantitative agreement with the enhancement of viscosity. Despite the rotational character of dielectric relaxation, the increase is consistent with a translational mass factor. For H/D substitution, the slow-down of the relaxation time is more pronounced and also shows a strong temperature dependence. In addition to the classical mass factor, the enhancement of the relaxation time for D216O can be described by an apparent temperature shift of 7.2 K relative to H216O, which is higher than the 6.5 K shift reported for viscosity. As this shift accounts for altered zero-point energies, the comparison suggests that the underlying thermally populated states relevant to the activation of viscous flow and dielectric relaxation differ.The mechanism of nitrobenzene hydrogenation on non-noble metals such as Ni is different from that previously reported for noble metals like Pt. The newly proposed pathway involves the initial dissociation of the two N-O bonds of nitrobenzene (Ph-NO2→ Ph-NO → Ph-N), leading to partial oxidation of the catalyst surface, followed by two successive hydrogenation steps (Ph-N → Ph-NH → Ph-NH2) that finally produce the functionalized aniline. Due to the oxophilic nature of non-noble metals like Ni, Co or Cu, the hydrogenation of the Ph-N intermediate and the removal of O in the form of water become the most energy demanding steps of the process. The strength of the interaction of O, H and N with different metals, and the preferential mode of adsorption of nitroarenes on clean and partially oxidized systems obtained from DFT calculations, are now used to propose an efficient non-noble metal catalyst that optimizes activity and selectivity.The initial stages of the nitrate radical (NO3) initiated oxidation of isoprene, in particular the fate of the peroxy (RO2) and alkoxy (RO) radicals, are examined by an extensive set of quantum chemical and theoretical kinetic calculations. It is shown that the oxidation mechanism is highly complex, and bears similarities to its OH-initiated oxidation mechanism as studied intensively over the last decade. The nascent nitrated RO2 radicals can interconvert by successive O2 addition/elimination reactions, and potentially have access to a wide range of unimolecular reactions with rate coefficients as high as 35 s-1; the contribution of this chemistry could not be ascertained experimentally. The chemistry of the alkoxy radicals derived from these peroxy radicals is affected by the nitrate moiety, and can lead to the formation of nitrated epoxy peroxy radicals in competition with isomerisation and decomposition channels that terminate the organic radical chain by NO2 elimination. The theoretical predictions are imith the measurements. The FZJ-NO3-isoprene mechanism is compared against the MCM v3.3.1 and Wennberg et al. (2018) mechanisms.5-8-defects are well-known in graphene and other 2D carbon structures, but not well-studied in one dimensional (1D) carbon materials. Here, we design a peanut-shaped carbon nanotube by assembling the 5-8-cage composed of carbon 5- and 8-membered rings, named 5-8-PSNT. https://www.selleckchem.com/products/rmc-4630.html Using first-principles calculations and molecular dynamics simulations, we find that 5-8-PSNT is not only thermally and dynamically stable, but also metallic. Moreover, its lattice thermal conductivity is only 95.87 W m-1 K-1, which is less than one tenth of the value of (6, 6) carbon nanotube that has a radius similar to that of 5-8-PSNT. A further analysis of the phonon properties reveals that the low lattice thermal conductivity of 5-8-PSNT arises from its low phonon group velocity, short relaxation time, large lattice vibrational mismatch and strong anharmonicity. These findings further suggest that a pentagon and an octagon as structural units can effectively modulate the properties of carbon materials.Electronic properties of molecules and carbon nanomaterials are usually affected by metal substrates. An electronic decoupling buffer layer is of importance to reveal their intrinsic properties. Here, the strength of electronic decoupling by a gold silicide buffer layer formed on Au(111) was studied using scanning tunneling microscopy/spectroscopy. The HOMO-LUMO gap of fullerene adsorbed on the buffer layer is approximately 3.0 eV, which is in between that on bare Au(111) and on a NaCl bilayer film, indicating a moderate decoupling.Information on pigment sizes in mural samples is a key factor in determining the suitable processes of possible restoration and conservation on ancient murals and is also significant for the investigation of a mural's historic value and analysis of its technical process. Thus, in this paper, the green painted layers composed of different pigment sizes were analyzed by laser-induced breakdown spectroscopy. First, a parametric study was undertaken to optimize the LIBS signal to noise ratio and decrease fluctuations. Then, the variation of LIBS signal with pigment size was studied on simulated mural samples. Finally, a classifiable model of pigment sizes was built by coupling with the PCA method and was successfully applied to classify pigment sizes on real mural pieces.The CO2-to-CO reduction by carbon monoxide dehydrogenase (CODH) with a [NiFe4S4] cluster is considered to be the oldest pathway of biological carbon fixation and therefore may have been involved in the origin of life. Although previous studies have investigated CO2 reduction by Fe and Ni sulfides to identify the prebiotic origin of the [NiFe4S4] cluster, the reaction mechanism remains largely elusive. Herein, we applied in situ electrochemical ATR-FTIR spectroscopy to probe the reaction intermediates of greigite (Fe3S4) and violarite (FeNi2S4). Intermediate species assignable to surface-bound CO2 and formyl groups were found to be stabilized in the presence of Ni, lending insight into its role in enhancing the multistep CO2 reduction process.